CN103400997A - Preparation method of carbon-modified and nickel-loaded sponge as anode material of hydroboron fuel cell - Google Patents
Preparation method of carbon-modified and nickel-loaded sponge as anode material of hydroboron fuel cell Download PDFInfo
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- CN103400997A CN103400997A CN2013103631364A CN201310363136A CN103400997A CN 103400997 A CN103400997 A CN 103400997A CN 2013103631364 A CN2013103631364 A CN 2013103631364A CN 201310363136 A CN201310363136 A CN 201310363136A CN 103400997 A CN103400997 A CN 103400997A
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- carbon
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000446 fuel Substances 0.000 title claims abstract description 20
- 239000010405 anode material Substances 0.000 title claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000006258 conductive agent Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 3
- 238000004070 electrodeposition Methods 0.000 abstract 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- 235000019270 ammonium chloride Nutrition 0.000 abstract 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 241000243142 Porifera Species 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241001346815 Spongia officinalis Species 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of carbon-modified and nickel-loaded sponge as the anode material of a hydroboron fuel cell. The preparation method comprises following steps: washing sponge for a plurality of times with acetone and ethanol, drying for 10 to 15 hours at the temperature of 110 to 130 DEG C, dissolving 100 to 150 mg of carbon and 500 mg of sodium dodecyl benzene sulfonate in 50 mL of distilled water, then subjecting the liquid to an ultrasonic treatment for 10 to 15 hours to obtain suspension liquid, soaking the washed sponge in the suspension liquid, allowing to stand still for 30 seconds, drying for 2 hours at the temperature of 110 to 130 DEG C, washing with a large amount of distilled water, then drying for 2 to 4 hours at the temperature of 110 to 130 DEG C so as to obtain a conductive carbon modified sponge, taking a mixed solution of NH4Cl with a concentration of 2 mol/dm<-3> and NiCl2 with a concentration of 0.1 mol/dm<-3> as the electro-deposition liquid, and then subjecting the sponge to an electro-deposition treatment for 4 to 6 hours with a current intensity of 10 mA so as to obtain the target product. The preparation method has the advantages of abundant and available Ni, carbon and sponge sources, low cost, large specific surface area and good conductivity of carrier carbon@Sponge, no use of binding agent and conductive agent, high catalytic activity, and stable performance, and solves the problem of small anode discharge current of hydroboron fuel cell.
Description
Technical field
That the present invention relates to is a kind of preparation method of anode material of direct borohydride fuel cell.
Background technology
Direct borohydride fuel cell (DBFC) is the fuel cell take boron hydride as fuel, NaBH
4The hydrogen storage material of hydrogen content very high (11wt.%), NaBH in theory
4Electrocatalytic Oxidation can be 8e-reaction, referring to (1) formula:
BH
4 -+8OH
-→BO
2 -+4H
2O+8e
- (1)
DBFC has very high energy density (specific energy is 9300Wh/kg), specific capacity (5668Ah/kg) and cell voltage, and (negative electrode is O
2The time 1.64V); NaBH
4Nonflammable, toxicity is low (unless eat, otherwise harmless), do not produce CO
2, NaBH in theory
4Can use non-platinum catalyst; NaBH
4Solution can serve as the coldplate that heat exchange medium carrys out cool batteries and need not be extra; The towing of the electric osmose of water can be used as cathode reactant, and like that needs are wetting and need not resemble hydrogen.These characteristics are very useful for design and the assembling of fuel cell.NaBH
4The electro-oxidizing-catalyzing agent mainly is divided into two large classes, and a class is the noble metals such as Pt, Pd, Au, Ir, and wherein the electro catalytic activity of Pt is the highest, but also is easy to occur NaBH
4Hydrolysis, referring to (2) formula:
NaBH
4+2H
2O→4H
2+NaBO
2 (2)
Can consult Kui Cheng; Dianxue Cao; Fan Yang; Dongming Zhang; Peng Yan; Jinling Yin; Guiling wang.Pd doped three-dimensional porous Ni film supported on Ni foam and its high performance towards NaBH
4Electrooxidation.Journal of Power Sources, 2013,242:141-147, and Cao Dianxue, Gao Yinyi, Wang Guiling, Miao Rongrong, Liu Yao.A direct NaBH
4-H
2O
2Fuel cell using Ni foam supported Au nanoparticles as electrodes.International Journal of Hydrogen Energy, 2010,35:807-813..
Summary of the invention
The object of the present invention is to provide and a kind ofly can improve sodium borohydride fuel cell anode activity, carbon with low cost is modified the preparation method of sponge nickel-loaded borohydride fuel battery anode material.
The object of the present invention is achieved like this:
(1) with acetone and ethanol, sponge is cleaned for several times, so its dry 10-15h under 110-130 ℃ is standby;
(2) get 100-150mg carbon and 500mg sodium dodecylbenzenesulfonate and be dissolved in 50mL distilled water, ultrasonic 10-15h obtains suspension;
(3) sponge that will clean is immersed in described suspension, after standing 30s, take out, after dry 2h under 110-130 ℃ with a large amount of distilled water washings, and then under 110-130 ℃ dry 2-4h, the carbon modification sponge of making conduction;
(4) get and contain 2mol dm
-3NH
4Cl and 0.1mol dm
-3NiCl
2Mixed solution as electrodeposit liquid, adopt the 10mA electric current, deposition 4-6h, finally make carbon and modify sponge nickel-loaded borohydride fuel battery anode material.
Described carbon is carbon nano-tube, active carbon, carbon black or carbon fiber.
Essence of the present invention is to adopt the battery structure of sodium borohydride fuel cell etc., with carbon, modifies sponge nickel-loaded (Ni@carbon@Sponge) and replaces the noble metal catalysts such as palladium, gold, silver, forms the anode of fuel cell.
The invention has the advantages that and utilize Ni@carbon@Sponge as the direct electrically optimized catalyst of sodium borohydride, not only the reserves of Ni, carbon and sponge are extremely rich and easy to get, and are cheap; The specific area of carrier carbon@Sponge is large, good conductivity; Do not use binding agent and conductive agent; And catalytic activity is high, stable performance.Solved the little problem of borohydride fuel anode discharge electric current.
Carbon in the present invention is preferably carbon nano-tube (MWNTs), and the product that obtains is Ni@MWNTs@Sponge electrode material.Described sponge comprises and contains commercial sponge, industrial sponge, renewable sponge and various porous elastic materials etc.
Embodiment
(1) with acetone and ethanol, sponge is cleaned for several times, so its dry 10-15h under 110-130 ℃ is standby;
(2) get 1030mg carbon nano-tube (MWNTs) and 500mg sodium dodecylbenzenesulfonate (SDBS) is dissolved in 50mL distilled water, ultrasonic 10-15h obtains suspension;
(3) sponge that will clean is immersed in described suspension, after standing 30s, take out, after dry 2h under 110-130 ℃ with a large amount of distilled water washings, and then under 110-130 ℃ dry 2-4h, the MWNTs modification sponge (MWNTs@Sponge) of making conduction;
(4) get and contain 2mol dm
-3NH
4Cl and 0.1mol dm-
3NiCl
2Mixed solution as electrodeposit liquid, adopt the 10mA electric current, deposition 4-6h, finally make carbon and modify sponge nickel-loaded borohydride fuel battery anode material (Ni@MWNTs@Sponge).
Carbon nano-tube in above-mentioned execution mode also can use active carbon, carbon black or carbon fiber to replace.Effect and the performance of resulting product are as follows:
1, take Ni@MWNTs@Sponge as work electrode, carbon-point is to electrode, take Ag/AgCl as reference electrode, at the NaOH of 2M and the NaBH of 0.10M
4Solution in, under the voltage of-0.7V vs.Ag/AgCl, the timing current density reaches 321mA/cm
2.
2, take Ni@active carbon@Sponge as work electrode, carbon-point is to electrode, take Ag/AgCl as reference electrode, at the NaOH of 2M and the NaBH of 0.10M
4Solution in, under the voltage of-0.7V vs.Ag/AgCl, the timing current density reaches 246mA/cm
2.
3, take Ni@carbon black@Sponge as work electrode, carbon-point is to electrode, take Ag/AgCl as reference electrode, at the NaOH of 2M and the NaBH of 0.10M
4Solution in, under the voltage of-0.7V vs.Ag/AgCl, the timing current density reaches 293mA/cm
2.
4, take Ni@carbon fiber@Sponge as work electrode, carbon-point is to electrode, take Ag/AgCl as reference electrode, at the NaOH of 2M and the NaBH of 0.10M
4Solution in, under the voltage of-0.7V vs.Ag/AgCl, the timing current density reaches 382mA/cm
2.
Claims (2)
1. a carbon is modified the preparation method of sponge nickel-loaded borohydride fuel battery anode material, it is characterized in that:
(1) with acetone and ethanol, sponge is cleaned for several times, so its dry 10-15h under 110-130 ℃ is standby;
(2) get 100-150mg carbon and 500mg sodium dodecylbenzenesulfonate and be dissolved in 50mL distilled water, ultrasonic 10-15h obtains suspension;
(3) sponge that will clean is immersed in described suspension, after standing 30s, take out, after dry 2h under 110-130 ℃ with a large amount of distilled water washings, and then under 110-130 ℃ dry 2-4h, the carbon modification sponge of making conduction;
(4) get and contain 2mol dm
-3NH
4Cl and 0.1mol dm
-3NiCl
2Mixed solution as electrodeposit liquid, adopt the 10mA electric current, deposition 4-6h, finally make carbon and modify sponge nickel-loaded borohydride fuel battery anode material.
2. carbon according to claim 1 is modified the preparation method of sponge nickel-loaded borohydride fuel battery anode material, and it is characterized in that: described carbon is carbon nano-tube, active carbon, carbon black or carbon fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310363136.4A CN103400997B (en) | 2013-08-20 | 2013-08-20 | Carbon modifies the preparation method of sponge nickel-loaded borohydride fuel battery anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310363136.4A CN103400997B (en) | 2013-08-20 | 2013-08-20 | Carbon modifies the preparation method of sponge nickel-loaded borohydride fuel battery anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103400997A true CN103400997A (en) | 2013-11-20 |
| CN103400997B CN103400997B (en) | 2015-09-30 |
Family
ID=49564578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310363136.4A Expired - Fee Related CN103400997B (en) | 2013-08-20 | 2013-08-20 | Carbon modifies the preparation method of sponge nickel-loaded borohydride fuel battery anode material |
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|---|---|
| CN (1) | CN103400997B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107509A (en) * | 2015-09-08 | 2015-12-02 | 徐金富 | Flexible loading type carbon fiber loaded CoB catalyst and preparation method thereof |
| CN105668711A (en) * | 2016-02-01 | 2016-06-15 | 浙江工商大学 | Sponge electrode for pollutant degradation as well as preparation and application thereof |
| CN106910898A (en) * | 2017-02-17 | 2017-06-30 | 哈尔滨工程大学 | Catalysis H2O2The preparation method of the carbon modifying foam carbon supported ni catalyst of electroxidation |
| CN110556545A (en) * | 2019-08-02 | 2019-12-10 | 重庆大学 | Nickel-based porous catalyst for direct oxidation of sodium borohydride |
| CN112599798A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | NaBH4Sponge and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290989A (en) * | 2007-04-18 | 2008-10-22 | 比亚迪股份有限公司 | Preparing method of catalyst electrode of fuel cell |
| US20110011772A1 (en) * | 2009-07-15 | 2011-01-20 | Stephen Raymond Schmidt | Nickel and Cobalt Plated Sponge Catalysts |
-
2013
- 2013-08-20 CN CN201310363136.4A patent/CN103400997B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101290989A (en) * | 2007-04-18 | 2008-10-22 | 比亚迪股份有限公司 | Preparing method of catalyst electrode of fuel cell |
| US20110011772A1 (en) * | 2009-07-15 | 2011-01-20 | Stephen Raymond Schmidt | Nickel and Cobalt Plated Sponge Catalysts |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107509A (en) * | 2015-09-08 | 2015-12-02 | 徐金富 | Flexible loading type carbon fiber loaded CoB catalyst and preparation method thereof |
| CN105668711A (en) * | 2016-02-01 | 2016-06-15 | 浙江工商大学 | Sponge electrode for pollutant degradation as well as preparation and application thereof |
| CN106910898A (en) * | 2017-02-17 | 2017-06-30 | 哈尔滨工程大学 | Catalysis H2O2The preparation method of the carbon modifying foam carbon supported ni catalyst of electroxidation |
| CN110556545A (en) * | 2019-08-02 | 2019-12-10 | 重庆大学 | Nickel-based porous catalyst for direct oxidation of sodium borohydride |
| CN112599798A (en) * | 2020-12-16 | 2021-04-02 | 北京大学 | NaBH4Sponge and preparation method thereof |
| CN112599798B (en) * | 2020-12-16 | 2021-12-07 | 北京大学 | NaBH4Sponge and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103400997B (en) | 2015-09-30 |
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Granted publication date: 20150930 |